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Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes

Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes

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CONNELLY, Neil, William GEIGER, Sherri LOVELACE, Bernhard METZ, Timothy PAGET, Rainer WINTER, 1999. Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes. In: Organometallics. 18(16), pp. 3201-3207. ISSN 0276-7333

@article{Connelly1999Reduc-13863, title={Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes}, year={1999}, doi={10.1021/om990089l}, number={16}, volume={18}, issn={0276-7333}, journal={Organometallics}, pages={3201--3207}, author={Connelly, Neil and Geiger, William and Lovelace, Sherri and Metz, Bernhard and Paget, Timothy and Winter, Rainer} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/13863"> <dc:creator>Paget, Timothy</dc:creator> <dc:creator>Metz, Bernhard</dc:creator> <dc:creator>Winter, Rainer</dc:creator> <dc:creator>Connelly, Neil</dc:creator> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:contributor>Metz, Bernhard</dc:contributor> <dcterms:title>Reduction of [ML(alkyne)2(η-C5R‘5)]+ (M = Mo or W, L = MeCN or CO, R‘ = H or Me, C5R‘5 = C5HPh4): Characterization of Radical Intermediates in the Reductive Coupling of Coordinated Alkynes</dcterms:title> <dc:contributor>Paget, Timothy</dc:contributor> <dcterms:bibliographicCitation>First publ. in: Organometallics 18 (1999), 16, pp. 3201-3207</dcterms:bibliographicCitation> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-29T09:37:56Z</dcterms:available> <dcterms:abstract xml:lang="eng">The complexes [M(NCMe)(RC2R)2(η-C5R‘5)]+ (M = Mo or W, R = Me or Ph; R‘ = H or Me, C5R‘5 = C5HPh4) undergo one-electron reduction to [M(NCMe)(RC2R)2(η-C5R‘5)], which rapidly lose acetonitrile to give the 17-electron complexes [M(RC2R)2(η-C5R‘5)]. The stability of [M(RC2R)2(η-C5R‘5)] depends on R and R‘; for R = Ph, the radical is sufficiently stable so that its reduction to the 18-electron anion [M(RC2R)2(η-C5R‘5)]- is detected in the cyclic voltammogram. Chemical reduction of [Mo(NCMe)(PhC2Ph)2(η-C5HPh4)]+ with [Co(η-C5H5)2] gives the air-sensitive solid [Mo(PhC2Ph)2(η-C5HPh4)], characterized as an alkyne-based radical by ESR spectroscopy, which gives [Mo(NCMe)(PhC2Ph)2(η-C5HPh4)]+ when treated with [Fe(η-C5H5)2]+ in acetonitrile. The carbonyl cations [M(CO)(RC2R)2(η-C5R‘5)]+ (M = Mo, W) undergo two sequential one-electron reductions, the first of which is reversible and gives the 19-electron species [M(CO)(RC2R)2(η-C5R‘5)]. The 19-electron radical [Mo(CO)(PhC2Ph)2(η-C5Me5)] has been characterized in solution by IR and ESR spectroscopy.</dcterms:abstract> <dc:language>eng</dc:language> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-29T09:37:56Z</dc:date> <dcterms:issued>1999</dcterms:issued> <dc:contributor>Winter, Rainer</dc:contributor> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/13863"/> <dc:creator>Lovelace, Sherri</dc:creator> <dc:creator>Geiger, William</dc:creator> <dc:contributor>Lovelace, Sherri</dc:contributor> <dc:rights>deposit-license</dc:rights> <dc:contributor>Geiger, William</dc:contributor> <dc:contributor>Connelly, Neil</dc:contributor> </rdf:Description> </rdf:RDF>

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